The controlled polymerization of (meth)acrylates under moderate conditions has been at the center of interest of numberous research groups for a long time..sup.1 For instance, an example of one approach developed in the 1980s was group transfer polymerization (GTP), although this approach requires expensive initiators and catalysts..sup.2 Moreover, coordinating ligands such as metallated alkoxide.sup.3 and lithium chloride.sup.4 have been used in the anionic polymerization of MMA, with adequate control being achieved only at temperatures &lt;-40 C. Other polymerization systems, such as catalytic chain-transfer polymerization,.sup.1 "living" free-radical polymerization,.sup.1,5 "metal-free,".sup.6 "coordinative,poly,".sup.7 "screened,".sup.8 "high-speed immortal".sup.9 and crown ether enhanced.sup.4a,10 anionic polymerization reactions, have been successful to differing degrees in the preparation of PMMA of narrow molecular mass distribution at moderate temperatures. n-Butyl acrylate has been anionically polymerized at 20.degree. C. by metal-free polymerization using tetrabutylammonium counterions,.sup.6 which is sensitive due to the instability of the initiators. A distinct improvement on this method is constituted by the anionic polymerization in the presence of tetraphenylphosphonium counter-ions..sup.11
1. Review Article: Davis, T., Haddleton, D., Richards, S. J. M. S. Rev. Macromol. Chem. Phys. 1994, C34, 243.
2. (a) Webster, O., Hertler, W., Sogah, D., Farnham, W. and RajanBabu, T. J. Am. Chem. Soc. 1983, 105, 5706; (b) Sogah, D., Hertler, W., Webster, O. and Cohen, G. Macromolecules 1988, 20, 1473.
3. Lochmann, L., Muller, A. Makromol. Chem. 1990, 191, 1657.
4. Teyssie, P., Fayt, R., Hautekeer, J., Jacobs, C., Jerome, R., Leemans, L., Varshney, S. Makromol. Chem., Macromol. Symp. 1990, 32, 61; (b) Wang, J., Jerome, R., Teyssie, P. Macromolecules 1994, 27, 4902.
5. (a) Otsu, T. and Tazaki, T. Polym. Bull. 1986, 16, 277; (b) Georges, M., Vereqin, R., Kazmaier, P., Hamer, G. Macromolecules 1993, 26, 2987; (c) Druliner, J. Macromolecules 1991, 24, 6079; (d) Mardare, D. and Matyjaszewski, K. Polymer Preprints (Am. Chem. Soc., Div. Polym. Chem.) 1993, 34, 566.
6. (a) Reetz, Mpoly, Knauf, T., Minet, U. and Bingel, C. Angew. Chem. Int. Ed. Engl. 1988, 27, 1371; (b) Reetz, M., Minet, U., Bingel, C. and Vogdanis, L. Polymer Preprints (Am. Chem. Soc., Div. Polym. Chem.) 1991, 32, 296; (d) Pietzonka, T. and Seebach, D. Angew. Chem. Int. Ed. Engl. 1993, 32, 716.
7. (a) Yasuda, H., Yamamoto, H., Yokota, K., Miyake, S. and Nakamura, A. J. Am. Chem. Soc. 1992, 114, 4908; (b) Yasuda, H., Yamamoto, H., Yamashita, Mpoly., Yokotd, Kpoly., Nakamura, A., Miyake, S., Kai, Y. and Kanehisa, N. Macromolecules 1993, 26, 7134.
8. Ballard, D., Bowles, R., Haddleton, D., Richards, S., Sellens, R. and Twose, D. Macromolecules 1992, 25, 5907.
9. (a) Sugimoto, H., Kuroki, M., Watanabe, T., Kawamura, C., Aida, T. and Inoue, S. Macromolecules 1993, 26, 3403; (b) Akatsuka, M., Aida, T. and Inoue, S. Macromolecules 1994, 27, 2820.
10. (a) Varshney, S., Jerome, R., Bayard, P., Jacobs, C., Fayt, R. and Teyssie, P. Macromolecules 1992, 25, 4457; (b) Wang, J., Jerome, R., Bayard, P., Baylac, L., Patin, M. and Teyssie, P. Macromolecules 1994, 27, 4615.
11. T. Hogen-Esch and A. Zagala, U.S. patent application Ser. No. 08/398,694.